GB2190670A - Inhibitors against corrosion by CO2 and H2S in water-in-oil emulsions - Google Patents
Inhibitors against corrosion by CO2 and H2S in water-in-oil emulsions Download PDFInfo
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- GB2190670A GB2190670A GB08712215A GB8712215A GB2190670A GB 2190670 A GB2190670 A GB 2190670A GB 08712215 A GB08712215 A GB 08712215A GB 8712215 A GB8712215 A GB 8712215A GB 2190670 A GB2190670 A GB 2190670A
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- alkenyl
- urea
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- alkyl
- inhibitors
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 32
- 238000005260 corrosion Methods 0.000 title claims abstract description 19
- 230000007797 corrosion Effects 0.000 title claims abstract description 19
- 239000000839 emulsion Substances 0.000 title claims abstract description 14
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 12
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002462 imidazolines Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000005326 tetrahydropyrimidines Chemical class 0.000 abstract 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 32
- 239000004202 carbamide Substances 0.000 description 32
- 239000000543 intermediate Substances 0.000 description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229960002969 oleic acid Drugs 0.000 description 5
- 235000021313 oleic acid Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- -1 aminopropyl Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000007762 w/o emulsion Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 2
- 229940033355 lauric acid Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- SMRRYNYQIFPENW-UHFFFAOYSA-N 1-(4,5-dihydroimidazol-1-yl)nonadec-3-en-1-amine Chemical compound C(=CCCCCCCCCCCCCCCC)CC(N)N1C=NCC1 SMRRYNYQIFPENW-UHFFFAOYSA-N 0.000 description 1
- NGKIIKNJVVBNNE-UHFFFAOYSA-N 11-methyldodecan-1-amine Chemical compound CC(C)CCCCCCCCCCN NGKIIKNJVVBNNE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- AEKNYBWUEYNWMJ-QWOOXDRHSA-N Pramiconazole Chemical compound O=C1N(C(C)C)CCN1C1=CC=C(N2CCN(CC2)C=2C=CC(OC[C@@H]3O[C@](CN4N=CN=C4)(CO3)C=3C(=CC(F)=CC=3)F)=CC=2)C=C1 AEKNYBWUEYNWMJ-QWOOXDRHSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Inhibitors against corrosion by CO2 and H2S in water-in-oil emulsions, containing a) an imidazoline or tetrahydropyrimidine derivative of the general formula I <IMAGE> and/or b) an acyclic intermediate thereof of the general formula II <IMAGE> where in the formulae I and II R<1> is C7- C22-alkyl or -alkenyl, n is 2 or 3 and x is an integer from 0 to 5 and in the formula I Y is H, C8-C18-alkyl or -alkenyl, or <IMAGE> in which R1, n and x have the above meanings, and in formula II Y is H, C8-C18-alkyl or -alkenyl, or <IMAGE> in which R1, n and x have the above meanings, are proposed.
Description
SPECIFICATION
Inhibitors against corrosion by CO2 and H2S in water-in-oil emulsions
The present invention relates to inhibitors against corrosion byCO2and H2S in water-in-oil emulsions, which inhibitors contain imidazoline ortetrahydropyrimidine derivatives and/or their acyclic intermediates.
The novel inhibitors are effective against corrosion by CO2 and H2S (acid gas) during crude oil production and the transport and storage of crude oils, which are generally in the form of water-in-oil emulsions, in particular salt water-in-oil emulsions.
It is known that, during oil production and the transportation and storage of the oil, a solution or dispersion of corrosion inhibitors is injected into the oil so that a protective layer is formed on the surface qfthe metal parts in contact with the oil.
German Published PatentApplication 2,846,979 describes corrosion inhibitorsforthis purpose which consist of an imidazoline salt, an oilsoluble solventforthe imidazoline salt and a hydrocarbon oil.
However, it has been found that, precisely in the case of salt water-containing water-in-oil emulsions (abbreviated to W/O emulsions below), imidazoline salts, as described in the stated publication, do not adequately suppress corrosion by H2S and 002. Another disadvantage is thatthese imidazolines have to be used with an oilsoluble solvent and a hydrocarbon oil.
German Published Patent Application 3,109,827 describes an inhibitor against corrosion by CO2 and H2S in
W/O emulsions. That inhibitor consists of a reaction productof A) Compounds ortheirsalts oftheformula Ill
orintermediatesoftheformula Illa
where R1 is C6-C22-alkyl or-alkenyl,X is -OH, -N H2 or
- 0 o II NH3 O=OPR(?R2 R2 is C4-C8-alkyl and n is 2, and B) elemental sulfur.
Although these inhibitors are in fact very effective, the factthat it is absolutely essential to incorporate sulfur makes their preparation energy-consuming, andtheiraction as an inhibitor is not optimum in all cases.
European Published Patent Application 0,103,737 describes inhibitors against corrosion by 002 and H2S in
W/O emulsions, the inhibitors containing
A) compounds oftheformula IV
or their acyclic intermediates of the formula IVa
where R1 is C6-C2ralkyl or -alkenyl, Xis -OH, -NH2 or
R2 is C4-C8-alkyl and n is 2 or3, and
B) maleamic acids of the formula V
where R3 is C8-C22-alkyl or-alkenyl, the molar ratio of componentAto component 8 being from 1 :4to4:1.
Although these inhibitors are already very effective, a further increase in the corrosion protection action of inhibitors is desirable.
It is an object of the present invention to provide novel inhibitors against corrosion by CO2 and H2S in W/O emulsions, these inhibitors being even more effective than the known inhibitors.
We have found that good results are achieved by inhibitors comprising
a) an imidazoline ortetrahydropyrimidine derivative of the general formula I
and/or
b) an acyclic intermediate thereof of the general formula II
where intheformulae land 11 R1 is C7-C22-alkyl or-alkenyl, n is 2 or3 andx is an integerfrom Oto 5 and in the formula lYisH,C8-C18-alkyl or-alkenyl,or
in which R1, n and xhavetheabove meanings, whereas in formula II Yis H, C8-C18-alkyl or alkenyl, or
in which R1, n and x have the above meanings.
In a preferred embodiment, the novel inhibitors comprise an imidazoline derivative of the general formula I where1 isC17-alkenyl, n is 2,x isO andY is hydrogen.
In another preferred embodiment, the novel inhibitors comprise an intermediate of the general formula where R1 is C15-C19-alkenyl, n is 2, xis an integerfrom 1 to 5 and Y is C13-alkenyl.
In the compounds ofthe general formulae I and II, R1 is C7-C22-alkyl or C7-C22-alkenyl. These radicals may be straight-chain or branched. The alkyl or alkenyl radicals are preferably of8 to 19, in particular 15 to 19, carbon atoms, and the alkenyl radicals may have one or more double bonds.
In both the general formulae land II Ycan be hydrogen, C8-C18-alkyl orC8-C18-alkenyl.
In the general formula l,Y may furthermore be
where R1, n and x have the above meanings.
In the general formula II, Y mayfurthermore be
where R1, n and x have the above meanings.
When Y is alkyl oralkenyl, C10-C18-alkyl and alkenyl are preferred.
The heterocycles and their acyclic intermediates are advantageously prepared as follows.
One mole of an imidazoline ortetrahydropyrimidine derivative or its acyclic intermediate is preferably reacted with one mole of urea and, if desired, one mole of an alkylamine at elevated temperatures,while stirring.The mixture is advantageously heated for about 8 hours at 160"C, ammonia being eliminated.
Thereafter, the mixture is heated for a further 2 hours at,for example,120 C 1200C and at,forexample, 27 mbar in order to complete the reaction. This procedure gives imidazoline ortetrahydropyrimidine derivatives ortheir acyclic intermediates in which Y is hydrogen oralkyl.
The imidazoline ortetrahydropyrimidine derivatives or their acyclic intermediates in which Y is ofthe above formulae can be prepared by heating, for example, 2 moles ofthe imidazoiine ortetrahydropyrimidine derivative or of the corresponding acyclic intermediate with, for example, one mole of urea. The mixture is advantageously stirred at about 160"C for about 8 hours, ammonia being eliminated. To complete the reac- tion,the mixture is then advantageously heated for a further 2 hours at 1 20"C and 27 mbar.
The acyclic intermediates ofthe general formula il may also be prepared in a single-vessel reaction. To do this, for example, 1 mole of a polyethyl(propylene)-amine, 1 mole of a fatty acid, 1 mole of urrea and, if required, 1 mole of an alkylamine are reacted at elevated temperatures. The reaction is advantageously carried out at a bout 1600C, heating being continued for8 hours. During this procedure, water and ammonia are eliminated. To complete the reaction,the mixture is advantageously heated for a further 2 hours atabout 27 mbar .This gives the intermediates ofthe general formula II whereY is hydrogen oralkyl.
Modification of the above procedures by a skilled worker permits the preparation of all inhibitors of the general formulae land II.
The novel inhibitors are added tothewater:Inoil emulsion in amounts of generallyfrom 2to 2000 ppm, preferablyfrom 3to 100 ppm, and particularlyfrom 5to 50 ppm, based on theweightoftheemulsion.
In the production of crude oil it may be advantageous to supply the inhibitorto a probe in such awaythat, for example when production is interrupted, a solution of the inhibitor in a suitable solvent is forced under pressure into the probe, batch addition being preferred. Examples of suitable solvents are liquid hydrocarbons such as crude oil condensate. The concentration of the inhibitor in the solution is in general from 5to 20% by weight and preferablyfrom 5to 10% byweight.
The Examples which follow illustrate the invention.
Example 1
139.6 g (0.6 mole) of 2-heptadecenyl-1 -aminoethylimidazoline (prepared form 1 mole of oleic acid and 1 mole of diethylenetriamine) are heated to about 80"C, and 24 g (0.6 mole) of urea are then introduced, after which the stirred mixture is heated at 1 60"C for 8 hours. During this procedure, ammonia is liberated. To complete the reaction, residual ammonia is removed inthecourse of a further 2 hours at 1200C and 27 mbar.
The productoftheformula I where R1 is C17H33r n is 2,x is0 and is H is obtained in quantitative yield.
Example 2 21.6 g (0.4 mole) of diethylenetriamine residue (main component triethylenetetramine and higher poly- amines and aminoethylethanolamine [more than 90% of the total mixture]; the amine residues are obtained in the distallation of diethylenetriamine; in the product, n is 2 and xis 1 - 5), 120.6 g (0.4 mole) oftall oil fatty acid (mixture offreefatty acids where alkyl is of 15to 19 carbon atoms,the main components being oleic acid, linoleic acid and linolenic acid (about 90%), 80 g (0.4 mole) of isotridecylamine and 24 g of (0.4 mole) of urea are combined and heated for8 hours at 160"C. During this procedure, ammonia escapes. The mixture is then stirred for a further 2 hours at 1 20"C and 27 mbar. The product of the general formula 11 where R1 is C16C1Sr n is 2,xis 1 - 5 and Yis C13H27, is obtained in quantitativeyield.
In the above Examples, acids of the formula R1COOH where R' has the above meanings, quite generally, can be reacted with diethylenetriamine, dipropylenetriamine, aminoethylethanolamine or aminopropyl ropanolamine. Examples ofsuitable acids ofthe formula B1COOH are 2-ethylhexanoic acid, nonanoic acid, oleic acid, stearic acid, lauric acid, elaidic acid and mixtures of natural fatty acids, such as coconutfattyacid ortallowfatty acid and tall oil fatty acid.
Particularly useful urea derivatives are those whose imidazoline component is derived from the C12-C20- carboxylic acids.
The advantage of imidazoline ortetrahydropyrimidine/urea derivatives used as novel inhibitors, and their acyclic intermediates, overthe corresponding nonderivatized compounds is thatthey provide better protection against corrosion. Corrosion protection is afforded against CO2 alone as well as against a combination of
CO2 and H2S.
Totestthe inhibitor compositions, a dynamictest (wheel test) was carried out; this is the method by which corrosion inhibitors are tested for oil and natural gas production.
The test coupons chosen were steel sheets measuring 130 mmx O mmx mm. These steel strips were rubbed with emery, degreased with toluene and weighed. The test medium used was mineral spiritwhich contained, in the form of an emulsion, saltwater having an NaCI content of 3%, based on water. The emulsion contained 50% by weight of saltwater and was saturated with H2S + CO2.
25 ppm, based on the weight ofthe emulsion, of inhibitorwerethen added.
The degreased and weighed sheets were then introduced into the emulsion and subjected to mechanical movement (40 rpm by means of a shaft rotating thetestvessels) at80"Cfor 16 hours.
The test strips were then cleaned with an inhibited acid degreased, dried, and the weighed to determine the weight loss. Evaluation was carried out in comparison with the blank value (experiment without the addition of an inhibitor).
The rate of corrosion and, from this, the percentage corrosion protection Z were calculated from there- sults:
where Go isthe rate of corrosion without an inhibitorand G1 is the rate with an inhibitor.
The results are shown in the Tables below.
Table 1
Test substance (formula I) Protection against CO2 [%] CO2/H2S [%]
Comparison (1) heptadecenylamino
ethylimidazoline 25 54
(2) tall oil fatty acid polyaminoethylimid
azoline 45 62
(3) lauric acid amino
ethylimidazoline < 10 37 Examplel (1) x urea 1:1 76 83
(2) xurea 1:1 79 86
Further Examples: (1) + urea + tridecylamine 1:1:1 81 82 (2) + urea + tridecylamine 1:1:1 83 84 (3)+ urea 1:1 65 76 (3) + urea + tridecylamine 1 :1:1 68 78
Comparison: (4) heptadecenyl-amino
propyl-2,4-dihydro
pyrimidine 22 58
(4) + urea 1:1 70 82
(4) + urea + tridecylamine
1:1:1 73 83 Table Test substance (formula II) Protection against CO2 [%] CO2/H2S [%]
Comparison (1)intermediate 18 52
(2) intermediate 32 68
(3) intermediate < 10 35
(4) intermediate 28 57 (1) intermediate + urea 1:1 72 82 (2) intermediate + urea 1:1 70 79 (3) intermediate + urea 1:1 78 80 (4) intermediate + urea 1:1 74 83 (1) intermediate + urea + tridecylamine 1:1:1 69 84 (2) intermediate + urea + stearylamine 1:1:1 74 81 (3) intermediate + urea + oleylamine 1:1:1 79 85 (4) intermediate + urea + tridecylamine 1:1:1 77 83
Table 111 Test substance (formula I) Protection against
CO2 [%] CO2/H2S [%] (1) +urea2: :1 74 84 (2) + urea 2:1 78 86 (3) + urea2:1 70 76 (4) + urea 2:1 75 81
Test substance (formula II) (1) intermediate + urea 2:1 69 85 (2) intermediate + urea 2:1 72 83 (3) intermediate + urea 2:1 67 80 (4) intermediate + urea 2:1 68 82
Table IV
Test substance (formula II) Protection against CO2[%] CO2/H2S [%]
Example2: (correspondsto
(2) intermediate + urea) 74 83 oleic acid + diethylenetriamine + urea 1:1:1 (=(1)intermediate+urea) 72 81 lauricacid + diethylenetriamine + urea 1:1:1 (= (3) intermediate + urea) 65 76 oleicacid + dipropylenetriamine + urea 1:1:1 (= (4) intermediate + urea) 76 79
Claims (4)
1. An inhibitor against corrosion by CO2 and H2S in water-in-oil emulsions, comprising
a) an imidazoline ortetrahydropyrimidine derivative of the formula I
and/or b) an acyclic intermediate thereof of the formula II
where intheformulae land II R1 is C7-C22-alkyl or-alkenyl, n is 2 or 3 and x is an integerfrom 0 to 5and in the formula I Y is H, C8-C18-alkyl or alkenyl, or
in which R1, n and x have the above meanings, whereas in the formula II Y is H, C8-C18-alkyl oralkenyl,or
in which R1, n and x have the above meanings.
2. An inhibitor as claimed in claim 1, comprising an imidazoline derivative of the formula where R' is C17-alkenyl, n is 2, xis 0 and Y is hydrogen.
3. An inhibitoras claimed in claim 1, comprising an intermediate of the formula II where R' isC15-Ca9- alkenyl, n is 2, x is an integer from 1 to 5 and Y is C13-alkenyl.
4. Awater-in-oil emulsion containing an inhibitorasclaimed in anyofclaims 1 to3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3617506 | 1986-05-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8712215D0 GB8712215D0 (en) | 1987-06-24 |
| GB2190670A true GB2190670A (en) | 1987-11-25 |
| GB2190670B GB2190670B (en) | 1990-02-14 |
Family
ID=6301564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8712215A Expired - Lifetime GB2190670B (en) | 1986-05-24 | 1987-05-22 | Inhibitors against corrosion by co2 and h2s in water-in-oil emulsions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2190670B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2279347A (en) * | 1993-06-22 | 1995-01-04 | Roger Liddle Jefferson | Urea derivatives and their use in treating water |
| RU2141543C1 (en) * | 1998-03-11 | 1999-11-20 | ОАО "Научно-исследовательский институт по нефтепромысловой химии" | Inhibitor of hydrogen-sulfide and/or carbonic acid corrosion |
| GB2351285A (en) * | 1999-03-15 | 2000-12-27 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
| GB2353793A (en) * | 1999-03-15 | 2001-03-07 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
| US6395225B1 (en) * | 1997-03-18 | 2002-05-28 | Elf Atochem S.A. | Sulphydryl acid and imidazoline salts as inhibitors of carbon corrosion of iron and ferrous metals |
| GB2385324A (en) * | 1999-03-15 | 2003-08-20 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
-
1987
- 1987-05-22 GB GB8712215A patent/GB2190670B/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS 61 :2939A 66(9): 37398Z * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2279347A (en) * | 1993-06-22 | 1995-01-04 | Roger Liddle Jefferson | Urea derivatives and their use in treating water |
| US6395225B1 (en) * | 1997-03-18 | 2002-05-28 | Elf Atochem S.A. | Sulphydryl acid and imidazoline salts as inhibitors of carbon corrosion of iron and ferrous metals |
| RU2141543C1 (en) * | 1998-03-11 | 1999-11-20 | ОАО "Научно-исследовательский институт по нефтепромысловой химии" | Inhibitor of hydrogen-sulfide and/or carbonic acid corrosion |
| GB2351285A (en) * | 1999-03-15 | 2000-12-27 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
| GB2353793A (en) * | 1999-03-15 | 2001-03-07 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
| GB2385324A (en) * | 1999-03-15 | 2003-08-20 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions |
| GB2351285B (en) * | 1999-03-15 | 2003-08-27 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions and methods |
| GB2385324B (en) * | 1999-03-15 | 2003-10-15 | Nalco Exxon Energy Chem Lp | Corrosion inhibiting compositions and methods |
| GB2353793B (en) * | 1999-03-15 | 2003-10-22 | Nalco Exxon Energy Chem Lp | Method of use of corrosion inhibitor compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2190670B (en) | 1990-02-14 |
| GB8712215D0 (en) | 1987-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930522 |